Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application

doi:10.1016/S1872-2067(21)63853-6

Abstract

Abstract:

Developing mild and efficient catalytic methods for the selective synthesis of amines is a longstanding research objective. In this respect, catalytic deoxygenative amide reduction has proven to be promising but challenging, as this approach necessitates selective C-O bond cleavage. Herein, we report the selective hydroboration of primary, secondary, and tertiary amides at room temperature catalyzed by an earth-abundant-metal catalyst, Zr-H, for accessing diverse amines. Various readily reducible functional groups, such as esters, alkynes, and alkenes, were well tolerated. Furthermore, the methodology was extended to the synthesis of bio- and drug-derived amines. Detailed mechanistic studies revealed a reaction pathway entailing aldehyde and amido complex formation via an unusual C-N bond cleavage-reformation process, followed by C-O bond cleavage.

Key words: Zirconium, Amide, Hydroboration, Amine, Catalysis

Bo Han, Jiong Zhang, Haijun Jiao, Lipeng Wu. Zirconium-hydride-catalyzed site-selective hydroboration of amides for the synthesis of amines: Mechanism, scope, and application[J]. Chinese Journal of Catalysis, 2021, 42(11): 2059-2067.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63853-6

https://www.cjcatal.com/EN/Y2021/V42/I11/2059

Figures/Tables 7

Scheme 1. Catalytic deoxygenative amide reduction and carbonyl hydroboration: (a) catalytic deoxygenative amide reduction using sensitive and hazardous metal hydrides or H2 under harsh reaction conditions; (b) catalytic hydroboration of carbonyls without C-O bond cleavage; (c) catalytic deoxygenative hydroboration of amides and the present methodology, featuring mild reaction conditions, a broad substrate scope, and detailed mechanistic understanding.

Table 1 Zirconium-catalyzed amide hydroboration: optimization of reaction conditions.

Entry	Catalyst	Catalyst amount (mol%)	Solvent	2a Yield * (%)
1	Cp₂ZrCl₂	5	THF	trace
2	Cp₂ZrHCl	5	THF	60
3	Cp₂ZrH₂	5	THF	70
4	Cp₂ZrH₂	10	THF	95
5	Cp₂ZrH₂	5	DCM	68
6	Cp₂ZrH₂	5	Et₂O	67
7	Cp₂ZrH₂	5	Toluene	38
8	Cp₂ZrH₂	5	CH₃CN	7
9	Cp₂ZrH₂	5	1,4-Dioxane	trace
10	Cp₂ZrH₂	5	neat	85

Fig. 1. (a) Operando IR spectra of the standard catalytic reaction process. 1H NMR spectra of reactions using (b) 0.16 mmol of 1a, 0.2 mmol Cp2ZrH2 in 2 mL chloroform-d for 1 h; (c) 0.2 mmol of 1a, 0.01 mmol Cp2ZrH2 in 2 mL chloroform-d for 1 h; (d) 0.2 mmol of 1a, 0.01 mmol Cp2ZrH2, 0.6 mmol HBpin in 2 mL chloroform-d for 1 h, followed by the addition of 0.2 mmol 4-phenylbenzaldehyde to the reaction solution; (e) 0.2 mmol of 1a, 0.01 mmol Cp2ZrH2, 0.6 mmol HBpin in 2 mL chloroform-d for 1 h, followed by the addition of 0.2 mmol HNEt2 to the reaction solution.

Fig. 2. M06L computed Gibbs free energy profiles (ΔG, kcal/mol) for the parent reaction between 1a and HBpin catalyzed by Cp2ZrH2.

Fig. 3. Proposed reaction mechanism of Cp2ZrH2-catalyzed hydroboration of amides.

Scheme 2. Reaction conditions: 0.2 mmol amide, HBpin (0.6 mmol, 3 equiv.), Cp2ZrH2 (5 mol%) in a reaction tube, stirred for 12-24 h at room temperature; isolated yields after treatment of the reaction mixture with 1 N HCl in ether are given. a Reaction was performed with additional 0.5 mL THF; b 60 °C for 48 h; c rt for 36 h, NMR yield; d 100 °C for 36 h, NMR yield.

Scheme 3. Reaction conditions: 0.2 mmol amide, HBpin (3 equiv. per amide bond), Cp2ZrH2 (5 mol%) in a reaction tube and stirred for 16 h at room temperature; isolated yields after treatment of the reaction mixture with 1 N HCl in ether. aReaction was performed at 60 °C; bisolated yields of amines.

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